Protective coating compositions containing natural-origin materials, and method of use thereof

ABSTRACT

A useful composition for protecting metal equipment from corrosion and/or other damage comprises 1) gilsonite, which is a mined asphalt; and/or some other natural-origin or naturally-derived resin, 2) a naturally-derived solvent such as d-limonene and/or other terpenes, and 3) a naturally-derived non-drying plasticizer such as fatty acid triglycerides. 4) Optionally, additives for controlling rheology, viscosity, lubricity, corrosion rates etc. can be added to obtain specific properties which may be desirable. The invention also relates to a method of preventing corrosion or other damage to metal equipment by applying the above-mentioned coating to the equipment by spraying, rolling and/or brushing.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] This invention relates to a class of novel compositions, whichare useful for protective coatings. More particularly, the inventioncomprises

[0003] 1) gilsonite, which is a mined asphalt and/or some othernatural-origin or naturally-derived resin,

[0004] 2) a naturally-derived solvent such as d-limonene and/or otherterpenes and

[0005] 3) a naturally-derived non-drying plasticizer exemplified by manyfatty acid triglycerides. Optionally, additives for controllingrheology, viscosity, lubricity, etc. can be added to obtain specificproperties which may be desirable.

[0006] What makes the instant invention particularly useful is that thematerial is either mined directly from the ground as an inert solid, orcontains naturally-derived, biodegradable, renewable materials. Thismakes it more “environmentally friendly” than many of the currentcoatings on the market, which contain petroleum solvents and/orpetroleum asphalt.

[0007] Another object of the instant invention is to provide analternative to more expensive coatings that may be used, such as epoxycoatings. The compositions are useful as protective coatings for paintedor unpainted metal surfaces, such as heavy equipment, bridges, piping,tanks, etc.

[0008] This invention also relates to a method of protecting said metalsurfaces, by brushing, rolling or spraying the above-mentionedcomposition onto the metal surfaces to be protected.

[0009] 2. Prior Art

[0010] 2.1. General Considerations

[0011] Corrosion of metal equipment and/or other metal objects is amulti-billion dollar a year problem. Corrosion causes failure of thecorroded object, leading to down time, expensive repairs or replacement,and potential liability if the failure occurs in such a way as to harmpeople.

[0012] Epoxy- and similar coatings may be useful in retarding corrosion,but they are in general not easy to apply, requiring substantial effortin surface protection and care, technical expertise and effort duringapplication. Epoxy and similar coatings also suffer from thedisadvantage of high cost. Therefore, what is desirable is an effective,low-cost coating.

[0013] It is well-known in the industry that asphalt tar, alone or incombination with gilsonite and/or certain other materials form the basisof protective coatings. These coatings are useful to help metal objectsto resist the corrosive effects of moisture.

[0014] However, many of the current coatings of this type on the marketcontain petroleum solvents and/or petroleum asphalt. This raisesconcerns when the coatings are used, due to the presence of suchenvironmentally-unfriendly components.

[0015] In particular, an especial concern of many users of protectivecoatings, is that during application some of the coating may fall on theground, yielding a violation of various environmental statutes whichprohibit spilling or dripping oil or petroleum-derived solvents on theground. Therefore, coatings which are derived from non-petroleum sourcesare desirable. It is the object of this invention to disclose suchcoating materials.

[0016] Another type of coating for this type involves gilsonite anddrying oils, such as tung oil, in combination with dryers, which areheavy metal catalysts. This type of material tends to become embrittledover time, leading to loss of adhesion. Also, the use of heavy-metaldryers defeats the purpose of utilizing otherwiseenvironmentally-friendly components such as naturally-derived oils.

[0017] 2.2. Prior Art—Discussion

[0018] In a series of patents by Burris and/or Burris et. al. (e.g. U.S.Pat. Nos. (this notation is hereinafter referred to as “US”) 4,073,659;4,094,696; 4,193,815; 4,282,037; 4,621,108; 5,811,477) variouscombinations of gilsonite, asphalt and/or high-boiling petroleumfractions and/or rubber are disclosed. Some of these mixtures areprepared as emulsions, with various emulsifiers and/or mixing sequences.These compositions find utility in a variety of applications, whichinclude coatings. However, all of these compositions havepetroleum-based solvents and/or asphalt. Therefore, a moreenvironmentally-friendly alternative is desirable, one that does notinvolve petroleum-based solvents and/or asphalt.

[0019] U.S. Pat. No. 4,600,635 to Wiercinski, et. al, disclosescompositions which comprise bitumen, oil, an ionomeric elastomer andgilsonite, and optionally a supportive and/or water-proofing membrane.These compositions are used in various water-proofing applications,including as water-proofing coatings. These compositions also sufferfrom the drawback that they contain oil and/or petroleum-based solvents.

[0020] U.S. Pat. Nos. 4,022,635 and 4,282,038 to Earing, disclose anencasing system to protect electrical components against water damage,which is one desirable characteristic among others possessed by thecompositions. The system comprises, among other things, gilsonite whichis modified by thermal depolymerization or by the addition of ahigh-viscosity process oil. These materials either have to beconsiderably heated prior to application, or contain process oils. Thus,someone desiring a coating to be applied at room temperature or below,or wanting to avoid using petroleum-derived products in their coating,would not find these compositions desirable.

[0021] U.S. Pat. No. 5,117,909 to Wilton, et al. discloses an oil- orgas well conduit sealant and method of placing this sealant where it canreduce leakage through the conduit in which it is placed. Thesecompositions comprise water or diesel fuel as a carrier liquid, anemulsifier, and particulate silica and/or gilsonite. A compositioncomprising water as the carrier for gilsonite will not result in auseful protective coating when sprayed, brushed or rolled on metalsurfaces, because gilsonite is not soluble in water to any appreciableextent. Therefore, a more suitable solvent is required for manyprotective coating applications. Likewise, the use of diesel fuel as thecarrier solvent will not satisfy the environmental constraints desiredin many applications.

[0022] U.S. Pat. No. 4,437,896 to Partanen discloses synthetic asphaltmixtures comprising selective blends of tall oil and/or tall oil pitchand gilsonite, and a process of preparing them. Optionally, otheringredients may be added to this mixture, such as aggregate, petroleumasphalt, reclaimed rubber, emulsifying agents, alcohols, fiber binder.The primary advantage to the Partanen compositions is that they are notrequired to have petroleum asphalt in them, or have reduced amounts ofit in them, so are potentially cheaper than petroleum-derivedcompositions. The primary applications are in paving.

[0023] To produce the Partanen mixtures, it is necessary to melt thegilsonite sometimes prior to and always after adding it to the tall oiland/or tall oil pitch, and the mixture is kept heated during processing.The resulting mixtures are generally solids at room temperature, and sowould not be useful for room-temperature or below-room-temperatureapplications.

[0024] Partanen does disclose liquid, or “cut-back” types ofcompositions, using the synthetic asphalt prepared as above, and dilutedwith alcohols, notably glycol ethers such as polyethylene glycols and/orpolypropylene glycols which are advantageous in that they are consideredmore environmentally-friendly than petroleum solvents. While this is so,these solvents tend to be rather expensive, so less-expensivealternatives are more desirable. Also, although the solvents are notpetroleum distillates or fractions, they are not of natural origin, andso their biodegradability can be an issue. It would be advantageous tohave coatings that would have solvents that are of natural origin.

[0025] U.S. Pat. No. 5,534,134 to Roder and Scriven disclose a pitchthat is low in polycyclic aromatic hydrocarbons (“PAH's”) and a methodfor making it. This composition is comprised of, among other things,coal tar pitch, petroleum pitch and gilsonite pitch. The coal tar is theprimary source of the PAH's. Handling compositions containing PAH's isconsidered to be hazardous, due to an increased risk of cancer. Theresultant pitch, due to it's lower coal tar pitch content, has loweredPAAH content than a coal tar pitch alone.

[0026] However, the combination still leaves much to be desired from anenvironmental standpoint. Therefore, it is still desirable to have aprotective coating that has a safer toxicological and/or environmentalprofile.

[0027] In the book Paints, Coatings and Solvents edited by Dieter Stoyeand Werner Freitag (Wiley-VCH), mention is made of combination paints ofGilsonite and drying oils. The merits and demerits of this type ofsystem have already been mentioned above.

SUMMARY

[0028] An object of the present invention is to provide a compositionthat yields a good protective coating when applied to metal substrates,but which utilizes natural-origin or naturally-derived raw materials.This object is fulfilled by a composition comprising:

[0029] 1. d-limonene or other natural-origin solvent(s) as the majorsolvent(s),

[0030] 2. gilsonite and/or some other naturally-derived resin as themajor hardening component,

[0031] 3. a naturally-derived non-drying plasticizer/softening agent,exemplified by fatty acid triglycerides, and

[0032] 4. other potential additives, such as

[0033] 1. Solid particles to enhance lubricity, such as molybdenumsulfide, graphite or fluorocarbon particles,

[0034] 2. Additional rust and/or corrosion inhibitors such as amines,amine salts, imidazolines, or corrosion inhibiting pigments, and/or

[0035] 3. Dispersing agents for the above.

[0036] The compositions are useful as protective coatings for painted orunpainted metal surfaces, such as heavy equipment, bridges, piping,tanks, etc.

[0037] This invention also relates to a method of protecting said metalsurfaces, by brushing, rolling or spraying the above-mentionedcomposition onto the metal surfaces to be protected.

DESCRIPTION OF THE INVENTION

[0038] This invention relates to a composition that is useful for use asa protective coating, and the use of that composition in protectingequipment. The composition comprises:

[0039] 1) a natural-origin solvent such as d-limonene as the majorsolvent, typically in the range of 25-95% by weight of the finalformulation,

[0040] 2) gilsonite and/or some other naturally-derived resinouscomponent as the major hardening component, typically 5-50% by weight ofthe final formulation,

[0041] 3) a naturally-derived non-drying plasticizer/softening agent,exemplified by fatty acid triglycerides, such as natural fats and oils,such that the plasticizer/naturally-derived resinous material ratio isin the range of 1/10 to 10/1, and

[0042] 4) other optional, potential special-purpose additives, such as

[0043] 1) Solid particles to enhance lubricity, such as molybdenumsulfide, graphite or fluorocarbon particles,

[0044] 2) Additional rust and/or corrosion inhibitors such as amines,amine salts, imidazolines, calcium salts of alkyl- or alkaril sulfonicacids or corrosion inhibiting pigments, and/or

[0045] 3) Dispersants for the insoluble components, and/or

[0046] 4) Coupling agents for special soluble additives.

[0047] The amount of these latter special-purpose components is expectedto be less than about 5-10% by weight of the total final film.

[0048] The invention utilizes a natural-origin solvent, such asd-limonene, derived from citrus- or pine processing, or other naturalorigin solvent. The d-limonene or other natural-origin solvent should bepresent in the mixture in the range of 25-95%, more preferably 40-75%,and in a most-preferred embodiment comprises 65-75% of the mixture. Ithas been observed that concentrations of many natural-origin resins muchhigher than about 25% tend to be very viscous, and handle and applypoorly.

[0049] In addition to d-limonene, other natural-origin solvents include,but are not limited to: amyl acetate, turpentine, pine oil,d,l-limonene, pine terpenes, and/or dimers or oligomers of these, andincluding mixtures and combinations of these.

[0050] The natural-origin solvent can potentially also be an alkyl esterderived from natural sources, including and preferably a mixture ofesters of varying hydrocarbon chain lengths and degrees of unsaturation.The alcohols used to make the esters include but are not limited tomethyl, ethyl, propyl, iso-propyl, butyl, isobutyl, tert-butyl, pentyl,hexyl, octyl, 2-ethylhexyl, glycerine, and longer-chain fatty alcohols.In a preferred embodiment, the alcohol is methyl or isopropyl. In amost-preferred embodiment, the alcohol is methyl.

[0051] The fatty acid(s) used as the fatty portion of potentially-usefulesters are selected from one or more of the following: acetic,propionic, butyric, pentanoic, hexanoic, 2-ethylhexanoic, heptanoic,octanoic, nonanoic, capric, caproic, undecanoic, lauric, myristic,palmitic, margaric, stearic, acachidic, behenic, lignoceric,myristoleic, palmitoleic, oleic, linoleic, linolenic, licosenoic behenicand erucic phthalic, isophthalic, terephthalic, maleic, fumaric, oxalic,malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacicacids and isomers and mixtures of these. The preferred embodiment acidsare fatty acid mixtures primarily in the C-8-C18 range, and arenaturally-derived.

[0052] Gilsonite and/or another naturally-derived resin is dissolved inthe natural-origin solvent, and provides the major portion of the finaldried film. Gilsonite is a naturally-occurring resin, soluble in manyorganic solvents. Other useful naturally-derived resins include, but arenot limited to: naturally-derived pitch, terpene resins and/or modifiedterpene resins such as terpene-phenolic resins, terpene-styrenic resins,terpene dimer resins; or rosin(s), gum rosins, modified rosins, rosinesters, etc. The naturally-derived resin in the instant inventioncomprises from about 5% to about 50% of the total formulated material.In a preferred embodiment, resin comprises from about 10 to about 25% byweight of the total formulation.

[0053] Gilsonite and many naturally-derived resins are typically hard,brittle materials, so it is advantageous to blend them with softeningagents. Therefore, the instant invention is rendered more useful by theaddition of a plasticizer, preferably of natural origin or otherwisenaturally-derived. The presence of the plasticizer renders the filmssubstantially less brittle, significantly increasing the life expectancythereby. A non-drying plasticizer is preferable, to avoid subsequentembrittlement of the resultant film.

[0054] Examples of useful natural-origin plasticizers include many fattyacid triglycerides, which are obtained from the food, paper, or othernatural-product processing industries. The plasticizer component ispresent in ratio to the resin in the range of 1 part plasticizer to 20parts naturally-derived resinous material, to 1 parts plasticizer to 1part naturally-derived resinous material. In a preferred embodiment, theplasticizer comprises from about 5% to about 20% of the final film.

[0055] The plasticizer which is preferred is an alkyl ester, as thesehave the required solubility, evaporation and environmental profiles.The alcohols used to make the esters include but are not limited tomethyl, ethyl, propyl, iso-propyl, butyl, isobutyl, tert-butyl, pentyl,hexyl, octyl, 2-ethylhexyl, glycerin, trimethylol propane, and/orlonger-chain fatty alcohols, or in general a substance containing fromabout 1 to about 20 carbon atoms, and having at least one hydroxylgroup.

[0056] Examples of fatty acids that find utility in the presentinvention as alkyl esters include caproic, enthanic, caprylic, capric,isodecyl, pelargonic, lauric, myristic, palmitic, oleic, linoleic,linolenic, stearic, isostearic, behenic, arachidic, arachidonic, erucic,azelaic, coconut, soya, tall oil, tallow, lard, neatsfoot, apricot,wheat germ, corn oil, cotton seed oil, ricinic, ricinoleic, rapeseed,palm kernel fatty acids, rosin acids, dimer acids, trimer acids, ozoneacids, diacids, triacids, combinations and mixtures of these, as well asother fatty acids preferably from natural sources, the fatty portion ofthe acid having average carbon chain lengths from about 6 to about 60.It is to be understood that there are other possible fatty acids whosealkyl esters could find utility in this invention, the above list isrepresentative, not exhaustive. It is also understood by those skilledin the art that mixtures and/or combinations of these will find utility.In fact, in a preferred embodiment, the plasticizers used aretriglycerides that include a mixture of fatty acids.

[0057] Another major characteristic of the fatty acids that make up thenatural-origin plasticizer is that they contain few components that havemore than two double carbon-carbon bonds in close proximity to eachother. The presence of many fatty acids that have more than two doublecarbon-carbon bonds in close proximity to each other causes theresultant mixtures to tend to crosslink within themselves over time,resulting in embrittlement and subsequent loss of adhesion.

[0058] Although the instant invention as outlined above has substantialwater-resisting properties, and provides a useful, inexpensiveprotective film for metal equipment, there are going to be situationswhere additional properties are desired. Therefore, the instantinvention is optionally improved upon by the addition of special-purposeadditives.

[0059] An example of such a kind of additive is the addition of solidsthat are used to enhance the lubricity of the resulting film. Examplesinclude but are not limited to graphite, molybdenum sulfide,poly-tetraflouroethylene (“PTFE”), ground waxes such as polyethylene,polypropylene, polyamid, or other polymeric waxes, or other solidlubricants.

[0060] In some cases, such additives tend to settle to the bottom of thestorage container, and re-dispersion may be difficult. In thatsituation, the addition of dispersants may enhance the storage stabilityof the product. Examples of such dispersants include but are not limitedto polyurethane polymeric dispersants such as EFKA 4010 by the LubrizolCorporation, polyacrylate polymeric dispersants such as EFKA 4010 by theLubrizol Corporation, and complex polycarbonic acid/amine oligomers suchas TEGO Dispers 630, fatty acid derivatives such as TEGO Dispers 700.Other dispersing agents may do, depending on the circumstances, as willbe understood by those skilled in the art.

[0061] Other potentially desirable additives may include specialcorrosion inhibitors. Examples include, but are not limited to, organiccorrosion inhibitors such as cationic amines or imidazolines, calciumsalts of certain sulfonic acids, as well as certain corrosion-inhibitinginorganic pigments such as iron oxide(s). Other corrosion inhibitors maydo, depending on the circumstances, as will be understood by thoseskilled in the art.

[0062] In a preferred embodiment, the optional corrosion inhibitor isnaturally-derived, and can also contribute to the plasticization effectthat is useful to enhance the coating life expectancy. Examples includesoya-based or tallow-based amines, their ethylene oxide adducts, and/orsalts thereof.

EXAMPLES

[0063] Examples 1 & 2 indicate that the present invention formsprotective coatings on metal surfaces.

Example 1

[0064] A protective coating was made comprising the followingingredients, with respective parts by weight: Gum Rosin “M” sold by AkzoNobel 1.06 d-limonene from orange processing 3.11 tallow diamine sold byTomah 0.73 premix with the below composition: 6.0 Zeco 11 gilsonite 55d-limonene 110

[0065] Zeco 11 is a grade of gilsonite sold by Ziegler Chemicals andMinerals Corp. Gum rosin M is a complex mixture containing rosin acidsand/or their esters. The resulting composition was placed in contactwith a clean, sanded steel plate, and showed excellent adhesion, was nottacky after drying, but was still somewhat soft, which allows for goodfilm flexibility.

Example 2

[0066] A protective coating was made comprising the followingingredients, with respective parts by weight: Gum Rosin “N” sold by AkzoNobel 1.0 d-limonene from orange processing 3.0 “E-18-2” ethoxylatedfatty amine 0.73 premix with the below composition: 6.0 Zeco 11gilsonite 55 parts by weight d-limonene 110 parts by weight

[0067] E-18-2 is an ethoxylated fatty amine sold by Tomah Products Corp.Gum Rosin M is a natural-origin rosin sold by Akzo Nobel Resins. Theresulting composition was placed in contact with a clean, sanded steelplate, and showed good adhesion, was not tacky after drying, but wasstill somewhat soft, which allows for good film flexibility.

Example 3

[0068] A protective coating was made comprising the followingingredients, with respective parts by weight: Tall Oil Pitch 1.0d-limonene from orange processing 4.0 premix with the below composition:6.0 Zeco 11 gilsonite 55 d-limonene 110

[0069] Tall oil pitch is a naturally-derived pitch from wood processing,and is sold by Arizona Chemical Company. It is a complex mixture ofacids, esters and alcohols, among other components. The resultingcomposition was placed in contact with a clean, sanded steel plate, andshowed good adhesion, was not tacky after drying, but was still somewhatsoft, which allows for good film flexibility.

Example 4

[0070] A protective coating was made comprising the followingingredients, with respective parts by weight: Terpene Resin 1100 1.0d-limonene from orange processing 3.0 premix with the below composition:6.0 Zeco 11 gilsonite 55 d-limonene 110

[0071] Terpene Resin TR 1100 is a modified terpene resin sold by ArizonaChemical Company. The resulting composition was placed in contact with aclean, sanded steel plate, and showed reasonably good adhesion, was nottacky after drying, but was still somewhat soft, which allows for goodfilm flexibility.

Example 5

[0072] A protective coating was made comprising the followingingredients, with respective parts by weight: Guni Rosin M 340d-limonene from orange processing 1701 molybdenum sulfide solidlubricant 300 Disperse 700 3 E-18-2 279

[0073] Disperse 700 is a dispersing agent sold by T. GoldschmidtCorporation. The mixture was sprayed on a salt and sand spreader toprotect from the weather during the summer months. The resultingcomposition showed good adhesion, was not tacky after drying, but wasstill somewhat soft, which allows for good film flexibility.

Example 6

[0074] A protective coating was made comprising the followingingredients, with respective parts by weight: Soybean Oil 0.75 premixwith the below composition: 6.0 Zeco 11 gilsonite 55 d-limonene 110

[0075] The resulting composition was placed in contact with a clean,sanded steel plate, and showed good adhesion, was not tacky afterdrying, but was still somewhat soft, which allows for good filmflexibility.

Examples 7 & 8

[0076] The composition of Example 6 was reproduced, but varying theamount of soybean oil, using 0.60 and 0.51 parts by weight,respectively. The resultant films, when dry, were progressively harder,but still had good adhesion and softness.

What is claimed is: 1) A useful composition for forming protectivecoatings, said coating composition comprising: a) a natural-originsolvent such as d-limonene as the major solvent, in the range of 25-95%by weight of the final formulation, b) gilsonite and/or othernatural-origin or naturally-derived resin as the major hardeningcomponent, comprising from about 5% to about 50% by weight of the finalformulation, c) a naturally-derived plasticizer/softening agent,exemplified by fatty acid triglycerides, such as natural fats and oils,such that the plasticizer to naturally-derived resinous material ratiois in the range of the range of 1 part plasticizer to 20 partsnaturally-derived resinous material, to about 1 part plasticizer to 1part naturally-derived resinous material, and the plasticizer isnon-drying, and d) other optional, potential special-purpose additives,such as Solid particles to enhance lubricity, such as molybdenumsulfide, graphite or fluorocarbon particles, Additional rust and/orcorrosion inhibitors such as amines, amine salts, imidazolines, orcorrosion inhibiting pigments, and/or Dispersants for the insolublecomponents, and/or Coupling agents for special soluble additives. 2) Thecomposition of claim 1, wherein the natural-origin solvent is derivedfrom citrus fruit or pine tree processing, posessing approximately 95%by weight d- and/or d-l limonene. 3) The composition of claim 1, whereinthe natural-origin solvent is selected from one or more of thefollowing: d-limonene, amyl acetate, turpentine, pine oil, d,l-limonene, pine terpenes, and/or dimers or oligomers of these, and/oralkyl esters of naturally-derived carboxylic acids. 4) The compositionof claim 1, wherein the natural-origin solvent is an alkyl esterpreferably derived from natural sources, including and preferably amixture of esters of varying hydrocarbon chain lengths and degrees ofunsaturation, and the alcohols used to make the esters include but arenot limited to methyl, ethyl, propyl, iso-propyl, butyl, isobutyl,tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl,glycerine and/orlonger-chain fatty alcohols. 5) The composition of claim 1, wherein thenatural-origin solvent is an alkyl ester preferably derived from naturalsources, including and preferably a mixture of esters of varyinghydrocarbon chain lengths and degrees of unsaturation, and thecarboxylic acids used to make the esters include but are not limited toone or more of the following: acetic, propionic, butyric, pentanoic,hexanoic, 2-ethylhexanoic, heptanoic, octanoic, nonanoic, capric,caproic, undecanoic, lauric, myristic, palmitic, margaric, stearic,acachidic, behenic, lignoceric, myristoleic, palmitoleic, oleic,linoleic, linolenic, licosenoic, behenic and erucic phthalic,isophthalic, terephthalic, maleic, fumaric, oxalic, malonic, succinic,glutaric, adipic, pimelic, suberic, azelaic, sebacic acids and/orisomers and/or mixtures of these. 6) The composition of claim 1, whereinthe resin component is gilsonite. 7) The composition of claim 1, whereinthe naturally-derived resinous component is selected from one or more ofthe following: gilsonite, naturally-derived pitch, terpene resins and/ormodified terpene resins such as terpene-phenolic resins,terpene-styrenic resins, terpene dimer resins; or rosin(s), gum rosins,modified rosins, rosin esters, etc., or mixtures or combinations ofthese. 8) The composition of claim 1 wherein the plasticizer, preferablyof natural origin, is a mixture of substantially non-drying fatty acidtriglycerides, obtained from the food, paper, or other natural-productprocessing industries. 9) The composition of claim 1 wherein theplasticizer, preferably of natural origin, is an alkyl ester, and thealcohol(s) used to make the esters include but are not limited tomethyl, ethyl, propyl, iso-propyl, butyl, isobutyl, tert-butyl, pentyl,hexyl, octyl, 2-ethylhexyl, glycerin, trimethylolpropane, and/orlonger-chain fatty alcohols, or in general a chemical whose molecularstructure includes from about 1 to about 20 carbon atoms, and at leastone hydroxyl group. 10) The composition of claim 1 wherein the fattyacid portion of the plasticizer includes but is not limited to one ormore of the following acids: caproic, enthanic, caprylic, capric,isodecyl, pelargonic, lauric, myristic, palmitic, oleic, linoleic,linolenic, stearic, isostearic, behenic, arachidic, arachidonic, erucic,azelaic, coconut, soya, tall oil, tallow, lard, neatsfoot, apricot,wheat germ, corn oil, cotton seed oil, ricinic, ricinoleic, rapeseed,palm kernel fatty acids, rosin acids, dimer acids, trimer acids, ozoneacids, diacids, triacids, combinations and mixtures of these, as well asother fatty acids preferably from natural sources, the fatty portion ofthe acid having average carbon chain lengths from about 6 to about 60,mixtures and/or combinations of these. 11) The composition of claim 1wherein an additive is added to enhance the protection of the substratefrom corrosion, examples of said additive include, but are not limitedto, organic corrosion inhibitors such as fatty amines such as soya-basedor tallow-based amines, their ethylene oxide adducts, and/or saltsthereof, imidazolines and/or salts thereof, calcium salts of certainsulfonic acids, as well as certain corrosion-inhibiting inorganicpigments such as iron oxide(s). 12) The composition of claim 1 whereinthe corrosion inhibiting additive contributes plasticity to theresultant film when applied to the substrate. 13) A method forprotecting heavy or light equipment from the elements, comprisingspraying, brushing or rolling a protective coating on the equipment,utilizing the coating compositions of claims 1-12.